JPH08217838A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermosetting resin composition having excellent toughness and peel strength without losing excellent properties of a bismaleimide resin and useful for a heat-resistant adhesive, etc., by including a specific ratio of aromatic bismaleimide, alkenylphenol and a polyalkylene phthalate. CONSTITUTION: This thermosetting resin composition contains (A) 100 pts.wt. of an aromatic bismaleimide of formula I [X is -CH2 , -C(CH3 )2 -, -SO2 -, -SO- or -O-] such as N,N'-4,4'-(3,3'-dimethyldiphenylmethane) bismaleimide, (B) 58-100 pts.wt. of alkenylphenol of formula II [R<1> and R<2> are each an allyl; Y is -CH2 - or -C(CH3 )2 -, etc.; n is 1-4] such as 2,3'-diallyl bisphenol A] and (C) 5-100 pts.wt. of a polyalkylene phthalate such as a polyalkylene phthalate having ortho-positioned and metha-positioned phthalate parts.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition using polyalkylene phthalate as a toughness modifier of a bismaleimide resin. Further, the present invention provides
The present invention relates to a cured product containing the thermosetting resin composition and a heat resistant adhesive.

[0002]

2. Description of the Related Art Bismaleimide (BMI) resins and cured products thereof are resins having high heat resistance and excellent workability. However, although the bismaleimide resin has excellent properties, it has the drawbacks of being hard and brittle, inferior in crack resistance, and extremely low in peel strength, and the application range of the bismaleimide resin is high-performance composite materials and electronic materials. As it spreads into the advanced technology field of b., The bismaleimide resin having higher performance, particularly the bismaleimide resin having excellent toughness which solves the above-mentioned drawbacks is demanded and various improvements have been made.

Examples of the organic synthetic polymer adhesives that have been conventionally used include adhesives containing epoxy resin, acrylic resin, fluorine resin, phenol resin, polyester resin, silicone resin and the like. However, although these adhesives are excellent in moldability such as molding temperature and adhesives at relatively low temperatures, they have problems in adhesive strength at high temperature, durability, and reliability.

In recent years, polyimide resins have been used as adhesives in the field of advanced technology, but high boiling point solvents such as amide solvents must be used, or molding must be performed at high temperatures. There is a problem in moldability and handling workability. Bismaleimide-based resin has high heat resistance as described above and has workability equivalent to that of epoxy resin.Bismaleimide-based adhesives on the market have high shear strength but very high peel strength. There is a problem of low. BACKGROUND ART Conventionally, various studies have been conducted on an epoxy resin which is a thermosetting resin in order to improve its toughness by making it a thermoplastic resin and a polymer alloy in order to improve the drawback of being brittle. For example, research by Tomoi et al. (Polymer Preprints, Japan Vol.43, No.3, p1233 (199) shows that adding polyester to an epoxy resin can make it tough without impairing the heat resistance and flexural modulus of the epoxy resin.
4)).

However, as a method of modifying a bismaleimide resin having higher heat resistance than an epoxy resin, a method of adding polyether sulfone (PES) or thermoplastic polyimide as a modifier is known. It is also known that a composition of a bismaleimide resin and an alkenylphenol has a high drape property and a high tack property and is excellent in workability. However, there is no known modifier that does not impair the properties of the original bismaleimide resin having high heat resistance and mechanical strength, and that can obtain high toughness. Furthermore, in applications that require higher performance, such as advanced technologies such as aviation materials and electric / electronic materials, there are few bismaleimide resins that still have satisfactory properties, and cured products with excellent performance can be obtained. It is further desired to develop a bismaleimide resin composition that can be used.

[0006]

The object of the present invention is to obtain a cured product having high toughness without impairing the excellent properties inherent to the cured product of the bismaleimide resin such as heat resistance and mechanical strength. The present invention provides a thermosetting resin composition and a cured product thereof. Another object of the present invention is to
An object of the present invention is to provide a heat-resistant adhesive having high shear strength and peel strength without impairing the excellent properties of a cured product of a bismaleimide resin such as heat resistance and mechanical strength. The present invention achieves at least one of the above objects.

[0007]

The present inventors have made diligent efforts to solve the above-mentioned problems of the prior art, and as a result, added a solvent by adding polyalkylene phthalate as a modifier to bismaleimide. It was found that a thermosetting resin composition having toughness can be obtained while maintaining heat resistance and mechanical properties without increasing the curing temperature to a high temperature of 300 ° C. or more, and has reached the present invention.

That is, according to the present invention, (A) 100 parts by weight of an aromatic bismaleimide and (B) an alkenylphenol 5
Provided is a thermosetting resin composition containing 8 to 100 parts by weight, and (C) 5 to 100 parts by weight of polyalkylene phthalate. A cured product obtained by heating and curing the above-mentioned thermosetting resin composition is provided. Further, (A) 100 parts by weight of aromatic bismaleimide, (B) alkenylphenol 58
To 100 parts by weight and (C) 5 to 100 parts by weight of polyalkylene phthalate are provided.

Then, (A) the aromatic bismaleimide 10
0 parts by weight, (B) alkenylphenol 58 to 100 parts by weight, and (C) polyalkylene phthalate 5-1
The present invention provides a heat-resistant adhesive, in particular a sheet-shaped heat-resistant adhesive, containing 100 parts by weight and impregnated into a carrier. Further, the polyalkylene phthalate is preferably a polyalkylene phthalate copolymer having phthalate moieties at the ortho and meta positions.

The thermosetting resin composition of the present invention will be described in detail below. The thermosetting resin composition of the present invention is obtained by toughening a bismaleimide resin using polyalkylene phthalate as a modifier.

The aromatic bismaleimide used in the thermosetting resin composition of the present invention can be obtained by a known method of reacting a corresponding aromatic diamine and maleic anhydride. As the aromatic bismaleimide, N, N'-m-
Phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 ' Examples thereof include-(3,3'-dimethylbiphenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and bismaleimide represented by the following general formula (1).

[0012]

Embedded image (In the formula, X is —CH ₂ —, —C (CH ₃ ) ₂ —, —S
Indicates O ₂ —, —SO— or —O—. )

Examples of the bismaleimide represented by the above general formula (1) include N, N'-4,4 '-(3,3'.
-Dimethyldiphenylmethane) bismaleimide, N,
N'-4,4 '-(3,3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-2,2-
Diphenylpropane bismaleimide, N, N'-4,
4'-diphenyl ether bismaleimide, N, N'-
3,3′-diphenylsulfone bismaleimide, N,
N'-4,4'-diphenylsulfone bismaleimide,
Examples thereof include N, N'-4,4'-diphenyl sulfoxide bismaleimide, N, N'-4,4'-diphenylsulfide bismaleimide, N, N'-4,4'-benzophenone bismaleimide, and the like. .

Among them, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-m-toluylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N'-4,4 '
-Diphenyl sulfone bismaleimide, N, N'-4,
4'-benzophenone bismaleimide or the like is preferable in terms of heat resistance of the resin after curing. In particular, N, N'-4,4'-
Diphenylmethane bismaleimide, N, N'-4,4 '
-Diphenyl ether bismaleimide, N, N'-m-
Toluylene bismaleimide, 2,2-bis [4- (4-
Maleimidophenoxy) phenyl] propane is preferred.

The above-mentioned aromatic bismaleimides may be used alone or in combination of two or more kinds. It is preferable to use a resin having a melting point of 170 ° C. or lower from the viewpoints of resin reactivity and mechanical properties such as good compatibility with alkenylphenol and reduction in melt viscosity of the thermosetting resin composition.

CH ₂ ═CHCH ₂ — used in the present invention
The alkenylphenol having an allyl group is a compound represented by the following general formula (2).

[0017]

Embedded image (In the formula, R ¹ or R ² each independently represents an allyl group, and Y is nil (none), —C (CH ₃ ) ₂ —, —
CH ₂ —, —C (CF ₃ ) ₂ —, and n represents an integer of 1 to 4. )

Here, R ^{1 and} R ² each independently represent an allyl group. The position of the allyl group on the aromatic ring is not particularly limited, but it is preferable that 1 to 4 groups are present at symmetrical positions on the ring. The reason for this is that the glass transition temperature of the resin after curing becomes high. Specifically, 2,
2'-diallylbisphenol A, 4,4'-dihydroxy-3,3'-diallyldiphenyl, bis (4-hydroxy-3-allylphenyl) methane, 2,2-bis (4-hydroxy-3,5-diallyl) Examples thereof include phenyl) propane and 2,2-diallylbisphenol F. Further, the reaction product of polyphenols with allyl chloride or allyl bromide has an allylation rate of phenolic OH.
50% or more and 100% or less with respect to the group, and the Claisen rearranged allyl group with respect to the phenolic OH group 20%
The above alkenylphenols can also be used.

The above-mentioned alkenylphenols may be used alone or in combination of two or more. 2,2'-
Diallyl bisphenol A, 2,2-bis (4-hydroxy-3,5-diallylphenyl) propane, 2,2 '
-Diallyl bisphenol F and the like are preferable because the glass transition temperature of the resin after curing is high, and in particular, 2,2'-diallyl bisphenol A and 2,2'-diallyl bisphenol F of the following formula (3) are compatible or cured products. Is preferable because of its high heat resistance temperature.

[0020]

Embedded image

The alkenylphenol used in the present invention is
It is preferably liquid or viscous at room temperature. This is because when the alkenylphenol is a solid, drape property and tackiness when the film-like and sheet-like adhesives are manufactured are deteriorated. The amount of alkenylphenol used in the present invention is 58 to 100 parts by weight based on 100 parts by weight of bismaleimide. The amount of the alkenylphenol compounded is in this range because if it is less than 58 parts by weight, the drape property and tackiness are deteriorated, and if it exceeds 100 parts by weight, the mechanical strength is deteriorated. It is preferably 58 to 93 parts by weight, and particularly preferably 58 to 86 parts by weight.

In the polyalkylene phthalate used in the present invention, the alkylene portion has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms. Specifically, poly (ethylene phthalate), poly (butylene phthalate), poly (propylene phthalate), poly (2,2-dimethylpropylene phthalate), poly (pentalene phthalate), poly (hexalene phthalate), etc. are exemplified. To be done. Among them, poly (ethylene phthalate), poly (propylene phthalate), and poly (butylene phthalate) are preferable in terms of mechanical strength.

The polyalkylene phthalates include 1,2-ethylene glycol, 1,3-propylene glycol, 1,3- (2,2-dimethyl) propylene glycol, 1,4-butylene glycol and 1,5 phthalic anhydride. -Alkylene glycols such as pentyl glycol and 1,6-hexyl glycol are added in an approximately equimolar or excess molar ratio, and heated in a nitrogen atmosphere at 180 ° C to 250 ° C with stirring to esterify and gradually increase the degree of vacuum. 10 To
It is manufactured by reaching rr or less and heating at a temperature of 240 ° C. to 280 ° C. for 1 hour or more. When a catalyst is used, it can be obtained by reacting with a Ti-based catalyst or the like.

The polyalkylene phthalate contains small amounts of low molecular weight parts. The number average molecular weight (Mn) is sensitive to the presence of this low molecular weight part, and as the molecular weight (MW),
It is preferable to use M _{GP C} (peak value of gel permeation chromatography using standard polystyrene). The average molecular weight (M _{GP C} ) of the polyalkylene phthalate is 3000 to 30000, especially 5000 to
It is preferably 30,000 in terms of the balance between toughness and heat resistance.

Further, as the polyalkylene phthalate, a polyalkylene phthalate copolymer having an ortho-position, a meta-position and / or a para-position phthalate moiety can be used. In particular, when used as a heat-resistant adhesive, it is preferable to use a copolymer in which the phthalate moiety is in the ortho position and the meta position in terms of maintaining heat resistance. Examples of such a polyalkylene phthalate copolymer include poly (ethylene phthalate-co-ethylene isophthalate), poly (butylene phthalate-co-butylene isophthalate), and poly (propylene phthalate) represented by the following formula (4). -Co-propylene isophthalate), poly (2,2-dimethyl propylene phthalate-co-2,
2-dimethylpropylene isophthalate) and the like, and in particular, poly (ethylene phthalate-co-ethylene isophthalate) is preferable from the viewpoint of maintaining heat resistance. When the copolymer of alkylene phthalate and alkylene isophthalate is used, the molar ratio of the isophthalate portion is 50 mol% or less, particularly 30 mol% or less, and further 20 mol% or less is preferable from the viewpoint of compatibility. .

[0026]

[Chemical 4]

The copolymer of polyalkylene phthalate and alkylene isophthalate is prepared by mixing phthalic anhydride and isophthalic acid in a molar ratio of 99: 1 to 50:50 to prepare 1,2-ethylene glycol, 1,3-propylene glycol,
Add alkylene glycols such as 1,4-butylene glycol, 1,5-pentyl glycol, and 1,6-hexyl glycol, heat to 180 ° C to 250 ° C in a nitrogen atmosphere and stir to esterify to gradually increase the degree of vacuum. 10
It is manufactured by allowing the temperature to reach Torr or lower and heating at a temperature of 240 ° C. to 280 ° C. for 1 hour or more. When a catalyst is used, it can be obtained by reacting with a Ti-based catalyst or the like. The average molecular weight (M _GPC ) of the polyalkylene phthalate copolymer is 3000 to 30000, especially 5000 to
It is preferably 30,000 in terms of the balance between toughness and heat resistance.

The amount of the polyalkylene phthalate used in the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the aromatic bismaleimide. If it is less than 5 parts by weight, the toughness is not improved, and if it exceeds 100 parts by weight, the heat resistance is lowered.

The thermosetting resin composition of the present invention does not need to use a curing catalyst, but may further contain a curing catalyst. The curing catalyst is not particularly limited, but dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide and the like are exemplified. Especially, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3 and the like are preferably exemplified. The amount of the curing catalyst used is 0.1 to 5 parts by weight, particularly 0.1% by weight, based on 100 parts by weight of the aromatic bismaleimide.
It is preferably 5 to 1 part by weight from the viewpoint of the balance between storage stability and curing speed.

In addition, in the thermosetting resin composition of the present invention, a filler, a plasticizer, a solvent and the like may be mixed if necessary in order to impart desired physical properties and viscous properties. .

The method for producing and curing the thermosetting resin composition of the present invention as described above may be the same as that for ordinary bismaleimide resin. For example, a predetermined amount of bismaleimide, alkenyl bisphenol, polyalkylene phthalate, and if necessary, an additive such as a curing catalyst are added and stirred and mixed to obtain the thermosetting resin composition of the present invention. The obtained composition is kneaded into the liquid phase of alkenylphenol without using a special solvent and is homogeneous. After that, for example, it is filled in a mold of a predetermined shape, and bismaleimide resin (compound)
180 to 25, for example, as necessary according to the type of
A cured product is obtained by heating to about 0 ° C. The obtained cured product forms a microphase-separated structure and is excellent in toughness without impairing heat resistance and mechanical properties.

The thermosetting resin composition of the present invention takes advantage of its excellent heat resistance and toughness to make use of electric / electronic materials, aviation and space materials (or composite materials), various adhesives, casting materials, and various materials. It can be suitably used for various applications such as molding materials.

One of the concrete examples thereof is a heat resistant adhesive. The heat resistant adhesive of the present invention contains the thermosetting resin composition of the present invention. One example of the production of the heat resistant adhesive of the present invention is, for example, mixing (A) bismaleimide, (B) alkenyl bisphenol, and (C) polyalkylene phthalate, especially poly (ethylene phthalate-co-ethylene isophthalate). In the form of a film-shaped heat-resistant adhesive obtained by molding the obtained heat-resistant adhesive composition into a film, a sheet-shaped heat-resistant adhesive obtained by impregnating a carrier such as woven cloth such as glass It may be in the form of. Since the heat-resistant adhesive of the present invention can be kneaded with the liquid phase of alkenyl bisphenol in either film form or sheet form, it is specially added to the components (A) to (C). It is possible to produce a sheet-shaped adhesive or prepreg without adding a solvent to
Excellent workability.

In the case of a film heat resistant adhesive, for example,
After mixing the components of the thermosetting resin composition of the present invention, a thickness of 10
~ 500μm sheet shape 140 ~ 180 ℃ if necessary
Then, it is heated to cure halfway and rolled by a calendar or the like to be molded.

In the case of a sheet adhesive, the base material used as a carrier is preferably a woven or non-woven glass base material because it has heat resistance and can be easily surface-treated. The glass base material may be a woven fabric such as a plain weave, a twill weave, a flat cloth weave, a four-sheet satin weave, and an eight-sheet satin weave,
Non-woven fabrics such as mats, yarns and chops may be used. Further, these base materials may be used alone or in combination of two or more kinds. In particular, when plain weave or mat is used as the base material, the effect is remarkable.

The heat-resistant adhesive of the present invention produced as described above is sandwiched between adherends and heat-cured for adhesion. As the adherend using the heat-resistant adhesive of the present invention,
Metals such as aluminum, iron and copper, FRP (fiber reinforced p
Composite materials such as lastic and fiber reinforced plastic) are preferable, and particularly when used as an adhesive agent of aluminum, iron, FRP, etc., the effect is remarkable. When the thermosetting resin composition of the present invention is used as an adhesive, it can be directly applied to the adhesive surface of the adherends, adhered to each other, and then heat-cured. The heat resistant adhesive obtained as described above is excellent in both shear strength and peel strength.

[0037]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to specific examples of the present invention. (Examples 1 to 11 and Comparative Example 1) Synthesis of polybutylene phthalate (PBP1-5) Phthalic anhydride and butylene glycol were charged in a molar ratio shown in Table 1 below, and about 0.65 g of a Ti-based catalyst (hydrolyzate of TiCl ₄ ) was added as a catalyst. The polybutylene phthalate (PBP1 to PBP1
5) was synthesized. Polymerization temperature and time, yield [%], average molecular weight M _GPC and number average molecular weight Mn (both GP
(Measured by C), Mw / Mn, glass transition temperature Tg ([° C.]
(Measured by DSC) is shown in Table 1.

[0038]

[Table 1]

2. Preparation and curing of thermosetting resin composition To 85 parts by weight of 2,2'-diallylbisphenol A, 1
Each of the PBPs 1 to 5 obtained in 1. was used as a modifier and added in an amount shown in Table 2, heated to 130 ° C., mixed and stirred to dissolve PBP, and then 4,4′-bismaleimidodiphenylmethane 10
0 part by weight was added, mixed and stirred to prepare a thermosetting resin composition of the present invention.

The prepared thermosetting resin composition was cast into a mold (preliminarily thinly coated with a release agent) preheated to 160 ° C. and cured under the following conditions. After the thermosetting resin composition was heated at 160 ° C. for 3 hours,
The temperature was raised to 0 ° C. for 1 hour, further raised to 200 ° C. for 2 hours, and then raised to 250 ° C. for 6 hours to perform curing. Further, it was constantly cooled from 250 ° C to 50 ° C at 25 ° C / h.

Fracture toughness value K _{IC of the} obtained cured product
(Measured with a 3-point bending test piece), bending strength (JIS K69
11), flexural modulus (based on JIS K6911), and glass transition temperature Tg (measured by ° C DSC).
Was measured, and the properties were visually observed. The results are shown in Table 2 below. In Table 2, poly (butylene phthalate) was not added, and the bismaleimide compound 100 was added.
An example of a composition consisting of only 1 part by weight and 85 parts by weight of diallyl bisphenol was designated as "control" (Comparative Example 1), and n in Table 2 is the number of test samples.

The molecular weight of aromatic bismaleimide when PBP was not added to FIG. 1 (indicated by ● in FIG. 1) and when 20 wt% of PBP was added (indicated by ○ in FIG. 1), The relationship between fracture toughness value K _IC , flexural modulus, flexural strength, and glass transition temperature is shown. Then, in FIG. 2, the molecular weight of PBP is 14,300 (PBP3 is indicated by a circle in FIG. 2) and PBP.
2 shows the relationship between the amount of PBP added and the fracture toughness value K _IC , flexural modulus, flexural strength, and glass transition temperature in the case of not adding (indicated by ● in FIG. 2).

[0043]

[Table 2]

As is clear from the results shown in Table 2 and FIG. 1, the characteristics of the cured product with respect to the molecular weight of the aromatic bismaleimide are that the fracture toughness value K _IC increases with the increase of the molecular weight, and the flexural modulus is the molecular weight. The tendency was to decrease with increasing.

Further, as is clear from the results shown in Table 2 and FIG. 2, the characteristics of the cured product with respect to the added amount of PBP are such that in the system in which the molecular weight of PBP is 14,300, the fracture toughness value increases as the added amount of PBP increases. K _IC increases, but bending strength,
The flexural modulus tended to decrease. Further, the cured product became opaque as the amount of addition increased. In addition, an uncertain endothermic peak was not observed in the DSC curve at the time of measuring Tg of each cured product.

(Examples 12 to 19 and Comparative Example 2) 1. Synthesis of polyethylene phthalate (PEP1-5) Phthalic anhydride and ethylene glycol were charged in a molar ratio shown in Table 3 below, and a Ti-based catalyst (hydrolyzate of TiCl ₄ ) was added as a catalyst in an amount shown in Table 3 below. Polyethylene phthalate (PEP1) was reacted under the reaction conditions shown in Table 3.
~ 5) was synthesized. Polymerization temperature and time, yield [%], average molecular weight M _GPC and number average molecular weight Mn (both measured by GPC), Mw / Mn, glass transition temperature T
Table 3 shows g (measured by [° C] DSC).

[0047]

[Table 3]

2. Preparation and curing of thermosetting resin composition To 85 parts by weight of 2,2'-diallylbisphenol A, 1
Each of the PEPs 1 to 5 obtained in 1. was added as the modifier in the amounts shown in Table 4, heated to 130 ° C., mixed and stirred to dissolve PBP, and then 100 parts by weight of 4,4′-bismaleimide-diphenylmethane. Was added, mixed and stirred to prepare the thermosetting resin composition of the present invention.

The prepared thermosetting resin composition was cast into a mold (preliminarily thinly coated with a release agent) preheated to 160 ° C. and cured under the following conditions. After the thermosetting resin composition was heated at 160 ° C. for 3 hours,
The temperature was raised to 0 ° C. for 1 hour, further raised to 200 ° C. for 2 hours, and then raised to 250 ° C. for 6 hours to perform curing. Further, it was constantly cooled from 250 ° C to 50 ° C at 25 ° C / h.

Fracture toughness value K _{IC of the} obtained cured product
(Measured with a 3-point bending test piece), bending strength (JIS K69
11), flexural modulus (based on JIS K6911), and glass transition temperature Tg (measured in ° C TMA).
Was measured, and the properties were visually observed. The results are shown in Table 4 below. In Table 4, an example of a composition consisting of 100 parts by weight of a bismaleimide compound and 85 parts by weight of diallyl bisphenol was used as a “control” (Comparative Example 2) without adding polyethylene phthalate, and n in Table 4
Is the number of test samples.

[0051]

[Table 4]

As is clear from the results shown in Table 4,
Fracture toughness value K of a cured product of the thermosetting resin composition of the present invention_{I c}
Is PEP4 compared to the cured product without PEP added.
(M _GPC= 18,200) Add about 20% by weight, about 80%
Increased. Bending strength is 20% by weight of PEP4
, Which was slightly lower than that of the control. Bending elasticity
The ratio is 20% by weight of PEP4 added system, compared to the control.
That was an increase of about 10%.

(Examples 20 to 22, Comparative Example 3) 1. Synthesis of poly (ethylene phthalate-co-ethylene isophthalate) (isophthalate unit 10 mol%) Phthalic anhydride, isophthalic acid and 1,2-ethylene glycol are charged, and a Ti-based catalyst (hydrolyzed product of TiCl ₄₎ is used as a catalyst. ) Was added and reacted to synthesize poly (ethylene phthalate-co-ethylene isophthalate) so that the isophthalate unit in the copolymer would be 10 mol%.

The resulting poly (ethylene phthalate-co-
The isophthalate unit of (ethylene isophthalate) was 10 mol%, the average molecular weight M _GPC = 19,500, the number average molecular weight Mn = 12,000, and Mw / Mn = 1.8. Polymerization time and temperature are 220 ° C / 120 minutes +28
0 ° C (1.7 Torr) / 330 minutes, yield 83.8
[%] And glass transition temperature Tg are 32 ([° C.] DSC
Was measured).

2. Preparation and Curing of Thermosetting Resin Composition 4,4′-Bismaleimidediphenylmethane 100 parts by weight, 2,2′-diallylbisphenol A 85 parts by weight Poly (ethylene phthalate-co-ethylene isophthalate) obtained in 1 (Isophthalate unit 10 mol%) was added as a modifier and mixed to prepare heat-resistant adhesives of the present invention (Examples 20 to 22).

[0056] The prepared heat-resistant adhesive, is impregnated into a plain weave glass fabric is a carrier (Arisawa Seisakusho Style101), the adhesive sheet of the adhesive sheet weight 415 g / m ² (in a glass carrier 70 g / m ²⁾ Was produced.

The obtained adhesive sheet was Al2024-T.
A 3 / Al2024-T3 adherend was pressure-bonded and adhered to obtain a test piece. Comparative Example 3 was carried out in the same manner as in Example 20 except that alkylene phthalate was not added. Drum peel strength (ASTM
D1781-76), tensile shear strength at 23 ° C.,
Tensile shear strength at 170 ° C. (according to ASTM D1002 (measured at 23 ° C. and 170 ° C.)) and glass transition temperature Tg (measured by ° C. DSC) were measured, and the properties were visually observed. The results are shown in Table 5 below.

[0058]

[Table 5]

Note) In the table, the amounts of the constituent components are parts by weight. ^{* 1} : Matrimid 5292A manufactured by Ciba-Geigy ^{* 2} : Matrimid 5292B manufactured by Ciba-Geigy From the above results, the effect of the present invention is clear.

[0060]

As described in detail above, according to the present invention, the thermosetting property having high toughness without impairing the excellent properties inherently possessed by the bismaleimide resin such as heat resistance and mechanical strength. A resin composition (cured product thereof) can be obtained. Furthermore, the adhesive containing the thermosetting resin composition of the present invention has heat resistance, mechanical strength, and the like, and also has excellent peel strength. The present invention has at least one of these effects.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the molecular weight of PBP and the fracture toughness value K _IC , flexural modulus, flexural strength, and Tg of the cured product of the thermosetting resin composition obtained.

FIG. 2 is a graph showing the relationship between the amount of PBP added and the fracture toughness value K _IC , flexural modulus, flexural strength, and Tg of the cured product of the thermosetting resin composition obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 7/00 JHL C09J 7/00 JHL 7/04 JHW 7/04 JHW

Claims (5)

[Claims] (1) 100 parts by weight of (A) aromatic bismaleimide, (B) 58 to 100 parts by weight of alkenylphenol,
And a thermosetting resin composition comprising (C) 5 to 100 parts by weight of a polyalkylene phthalate. 2. The thermosetting resin composition according to claim 1, wherein the polyalkylene phthalate is a polyalkylene phthalate copolymer having phthalate moieties at ortho and meta positions. 3. A cured product obtained by heating and curing the thermosetting resin composition according to claim 1. 4. (A) 100 parts by weight of aromatic bismaleimide, (B) 58 to 100 parts by weight of alkenylphenol,
And (C) 5 to 100 parts by weight of polyalkylene phthalate, a heat resistant adhesive film. 5. (A) 100 parts by weight of aromatic bismaleimide, (B) 58 to 100 parts by weight of alkenylphenol,
And (C) 5 to 100 parts by weight of polyalkylene phthalate, which is impregnated in a carrier to obtain a heat-resistant adhesive.